CN105093866B

CN105093866B - Electrophotography component, handle box and electronic photographing device

Info

Publication number: CN105093866B
Application number: CN201510250088.7A
Authority: CN
Inventors: 山口壮介; 山田真树; 有村秀哉; 山内一浩; 西冈悟
Original assignee: Canon Inc
Current assignee: Canon Inc
Priority date: 2014-05-16
Filing date: 2015-05-15
Publication date: 2019-10-11
Anticipated expiration: 2035-05-15
Also published as: US20150331341A1; JP2015232700A; EP2950153B1; JP6486188B2; US9639009B2; CN105093866A; EP2950153A1

Abstract

The present invention relates to electrophotography component, handle box and electronic photographing devices.The present invention, which provides, is reducing high conductivity electrophotography component, handle box and the electronic photographing device that high-quality electrophotographic image is contributed to form while ionic conductive agent exudation.Therefore, electrophotography component according to the present invention includes conductive shaft core and conductive layer, and wherein conductive layer includes the resin and anion by nitrogenous aromatic heterocyclic cation and the compound synthesis that can be reacted with nitrogenous aromatic heterocyclic cation；There are two the substituent groups for being bonded to hydroxyl for nitrogenous aromatic heterocyclic cation tool；And the substituent group for being bonded to hydroxyl is bonded to the nitrogen-atoms of the nitrogenous heteroaromatic of nitrogenous aromatic heterocyclic cation.

Description

Electrophotography component, handle box and electronic photographing device

Technical field

The present invention relates to including the electrophotography component in electronic photographing device, and including the electrophotography structure The handle box and electronic photographing device of part.

Background technique

In electronic photographing device (electro photography type electrophotographic copier, facsimile machine and printer etc.), electrofax Electrifier frame, photoreceptor (hereinafter also referred to as " Electrifier frame, photoreceptor ") is charged by charging roller, and is exposed to laser beam etc., thus photosensitive Electrostatic latent image is formed on component.Then the toner supplying roller of the toner in developer container and toner control member are coated on On developer roll.Then, toner is delivered to developing regional with developer roll.With the toner being delivered to developing regional, make Contact portion of the electrostatic latent image between Electrifier frame, photoreceptor and developer roll on Electrifier frame, photoreceptor or development near it.Then, Electrifier frame, photoreceptor On toner be transferred in recording sheet by transfer unit, and by heating and pressure fixing, while being gone with cleaning unit Except toner remaining on Electrifier frame, photoreceptor.

In this electron-like camera installation, electrophotography component that is with conductive layer and being used for developer roll or charging roller Should have about 10 by control⁵-10⁹The resistance of Ω.Entire electrophotography component should have uniform, steady in a long-term Electric conductivity.By conductive agent, for example, such as carbon black conductive particle or if quaternary ammonium salt plasma conductive agent is by scheduled conduction Property assign conductive layer.Advantageously, the electron conduction roller comprising the conductive particles such as such as carbon black etc. hardly pollutes and the electricity Other components of subconductivity roller contact.On the other hand, such as carbon black conductive particle is difficult to be uniformly dispersed, and is not easy Prevent part that there is the generation at low-resistance position.Compared with electron conduction roller, the ionic conductivity comprising ionic conductive agent Roller can reduce the uneven resistance for being attributed to the uneven dispersion of conductive agent, and hardly have low-resistance portion with part Position.The developer on Electrifier frame, photoreceptor can be made equably to develop for this purpose, being used as such ionic conductivity roller of developer roll, and used The such ionic conductivity roller for making charging roller can make the uniformly electrification of Electrifier frame, photoreceptor.

On the other hand, ionic conductive agent has migration, therefore is easy to be migrated from conductive layer thus from it after being used for a long time Surface exudation.Ionic conductive agent via the migration of conductive layer can change electrophotography component through when electric conductivity.From conduction The ionic conductive agent of layer surface exudation may be attached to the surface of Electrifier frame, photoreceptor contacted with electrophotography component etc., to drop The quality of low electrophotographic image.

In order to solve this problem, Japanese Patent Application Laid-Open 2011-118113 discloses the ionic liquid having there are two hydroxyl Body makes the ionic liquid be fixed to polyurethane resin composition to reduce the exudation of ionic conductive agent.

Japanese Patent Application Laid-Open 2011-32397 is disclosed by making the ionic liquid containing reactive hydrogen via carbamic acid Ester bond and be bonded to resin or add the polymerizate of the ionic liquid of the alkenyl containing unsaturated ethylene and preparing it all has The durable antistatic resin of antistatic property.

Present inventor has performed study and find that comprising tool, ion is led there are two in the conductive layer of the ionic conductive agent of hydroxyl Electric agent is fixed to conductive layer, to reduce exudation of the ionic conductive agent from conductive layer.However, the fixation of ionic conductive agent can reduce The electric conductivity of conductive layer, so that electric conductivity needed for cannot obtaining electrophotography component, thus makes the product of electrophotographic image Matter reduces.

Summary of the invention

The present invention is intended to provide contributing to form high-quality electrofax figure while reducing the exudation of ionic conductive agent The high conductivity electrophotography component of picture.

In addition, the present invention is also directed to steadily export the electronic photographing device of high-quality electrophotographic image, with It and include the handle box in such electronic photographing device.

The present inventor has been carried out extensive research to the realization purpose.As a result, the inventors discovered that, it is including with having In the electrophotography component of the conductive layer of the ionic conductive agent preparation of specific structure, ionic conductive agent hardly oozes out, and High conductivity is obtained, thus the present inventor realizes the present invention.

According to an aspect of the present invention, the electrophotography component including conductive shaft core and conductive layer is provided, wherein institute Stating conductive layer includes to be closed by nitrogenous aromatic heterocyclic cation and the compound that can be reacted with nitrogenous aromatic heterocyclic cation At resin and anion；There are two the substituent groups for being bonded to hydroxyl for nitrogenous aromatic heterocyclic cation tool；Condition is, when When nitrogenous heteroaromatic in nitrogenous aromatic heterocyclic cation only has a nitrogen-atoms, a substituent group is bonded to the nitrogen Atom, and another substituent group is bonded to the carbon atom of nitrogenous heteroaromatic, and when in nitrogenous aromatic heterocyclic cation Nitrogenous heteroaromatic have more than two nitrogen-atoms when, substituent group is bonded to two nitrogen originals in nitrogenous heteroaromatic Son.

According to another aspect of the present invention, the electrophotography component including conductive shaft core and conductive layer is provided, wherein The conductive layer includes resin and anion with the structure indicated by structural formula (1):

Wherein Z indicates the cation matrix comprising the nitrogenous heteroaromatic of cationic；A₁And A₂The company of each independently representing It connects group and is bonded to the nitrogen-atoms of the nitrogenous heteroaromatic of the cationic in Z；Condition is, when the nitrogenous fragrance of cationic When race's heterocycle only has a nitrogen-atoms, A₁And A₂One of be bonded to the nitrogen-atoms, and A₁And A₂Another be bonded to cation Property nitrogenous heteroaromatic in carbon atom, and when the nitrogenous heteroaromatic of cationic has more than two nitrogen-atoms When, A₁And A₂Two nitrogen-atoms being bonded in the nitrogenous heteroaromatic of cationic；And B₁And B₂Each independently represent hydroxyl Hydrogen atom in base and the residue that can be reacted with the compound of the atomic reaction of hydrogen of hydroxyl.

According to another aspect of the present invention, handle box is provided, the main body of electronic photographing device is detachably mounted to, and And including at least one of charging member and developer bearing member, wherein charging member or developer bearing member are the electricity Component is used in son photograph.

According to another aspect of the present invention, electronic photographing device is provided comprising electrophotographic photosensitive element, charging member And developer bearing member, wherein charging member or developer bearing member are the electrophotography component.

The present invention can provide high conductivity electrophotography components, if by with specific structure cation and can It is included in conductive layer, then has while reducing the exudation of ionic conductive agent with the resin of the compound synthesis of cationoid reaction Help to form high-quality electrophotographic image.The processing that can be stably formed high-quality electrophotographic image can also be provided in the present invention Box and electronic photographing device.

From the description of following exemplary embodiment with reference to attached drawing, further characteristic of the invention will become aobvious and easy See.

Detailed description of the invention

The A of Fig. 1 is the concept map for showing the example of electrophotography component according to the present invention.

The B of Fig. 1 is the concept map for showing another example of electrophotography component according to the present invention.

The C of Fig. 1 is the concept map for showing another example of electrophotography component according to the present invention.

Fig. 2 is the schematic diagram for showing the construction of the example of handle box according to the present invention.

Fig. 3 is the schematic diagram for showing the construction of the example of electronic photographing device according to the present invention.

The A of Fig. 4 is to show measuring device for measuring the current value of electrophotography component according to the present invention (wherein Electrophotography component follows other rollers to rotate) construction schematic diagram.

The B of Fig. 4 is the construction shown for measuring the measuring device of the current value of electrophotography component according to the present invention Schematic diagram.

Specific embodiment

Now, the preferred embodiments of the invention will be described in detail with reference to the attached drawings.

Electrophotography component according to the present invention includes conductive shaft core and conductive layer, and wherein conductive layer includes by nitrogenous The resin of aromatic heterocyclic cation and the compound synthesis that can be reacted with nitrogenous aromatic heterocyclic cation, and yin from Son；There are two the substituent groups for being bonded to hydroxyl for nitrogenous aromatic heterocyclic cation tool；And it is bonded to the substituent group bonding of hydroxyl To the nitrogen-atoms of the nitrogenous heteroaromatic of nitrogenous aromatic heterocyclic cation.

An embodiment of electrophotography component is in the C of the B and Fig. 1 of A, Fig. 1 of Fig. 1 according to the present invention It shows.As shown in the A of Fig. 1, electrophotography component 1 according to the present invention may include conductive shaft core 2, and be arranged outside it The elastic layer 3 in week.In this case, elastic layer 3 is the conductive layer prepared with resin according to the present invention.Selectively, elastic The surface of layer 3 can have superficial layer 4 as shown in the B of Fig. 1.In this case, conductive layer according to the present invention can be used for any Elastic layer 3 and superficial layer 4.

In addition, as shown in the C of Fig. 1, electrophotography component according to the present invention have the elastic layer 3 configured in order, in The three-decker of interbed 5 and superficial layer 4 can have the multilayered structure including multiple middle layers 5.In this case, according to this The conductive layer of invention can be used as any elastic layer 3, middle layer 5 and superficial layer 4.

Mandrel 2 plays the role of the electrode and supporting member of electrophotography component 1.Mandrel 2 is made of following: as aluminium, The metal or alloy such as copper alloy and stainless steel；It is coated with the iron of chromium or nickel；Or such as electric conductivity synthetic resin conductive material.Core Axis 2 can be solid or can be hollow.

In electrophotography component according to the present invention, conductive layer includes by nitrogenous aromatic heterocyclic cation and can be with The resin and anion of the compound synthesis of the cationoid reaction.In the present invention, the resin being contained in conductive layer is led with ion It is prepared by electric agent.Ionic conductive agent indicates to be used to prepare the material of the resin being contained in conductive layer, and the material is also not and energy It is enough to be reacted with the compound of cationoid reaction.Cation indicates to be contained in ionic conductive agent and by structural formula (2) expression Cation:

Wherein Z indicates the cation matrix comprising the nitrogenous heteroaromatic of cationic；Nitrogen atom bonding in Z is to A₁With A₂；A₁And A₂Each independently represent linking group；A₁And A₂The nitrogen-atoms being respectively bonded in Z；And H indicates that the hydrogen of hydroxyl is former Son.

The substituent group for being bonded to hydroxyl can have alkylene oxide structure between the hydrogen atom and nitrogen-atoms of hydroxyl.

Alkylene oxide structure can be indicated by formula (I) or (II):

Wherein * indicates the binding site with the hydrogen atom of hydroxyl；* indicates the binding site with nitrogen-atoms；A is 1 or more And 9 integer below；And b is 1 or more and 4 integers below.

In structural formula (2), Z may include being selected from cationic imidazole skeleton and cationic pyridine skeleton at least A kind of skeleton.

Cation with the structure indicated by structural formula (2) and can be with the compound of the cationoid reaction for for making The basic material of the standby resin with the structure indicated by structural formula (1).The representation indicated by structural formula (1) is according to this hair Bright cation and the structure after capable of being reacted with the compound of the cationoid reaction.It include to have for conductive layer of the invention By the resin and anion of the structure that structural formula (1) indicates.

Wherein Z indicates the cation matrix comprising the nitrogenous heteroaromatic of cationic；A₁And A₂The company of each independently representing It connects group and is bonded to the nitrogen-atoms of the nitrogenous heteroaromatic of the cationic in Z；And B₁And B₂Each independently represent hydroxyl The hydrogen atom of base and the residue that can be reacted with the compound of the atomic reaction of hydrogen of hydroxyl.

B₁And B₂It respectively may include at least one structure selected from urethane bond and ehter bond.In the present invention, cation Property organic group indicate the Z in the structural formula (1) for including in the resin prepared after the cationoid reaction that is indicated by structural formula (2).

In formula (1), linking group A₁And A₂Alkylene oxide structure can be each independently represented.

Alkylene oxide structure can be for by the structure of formula (III) or (IV) expression:

Wherein * * * indicates the binding site with residue；* * * indicates the binding site with nitrogen-atoms；C be 1 or more and 9 with Under integer；And d is 1 or more and 4 integers below.

In structural formula (1), Z can be for selected from glyoxaline cation (cationic imidazole skeleton) and pyridylium At least one cation of (cationic pyridine skeleton).

In structural formula (1), B₁Or B₂It may include the hydrogen atom of hydroxyl and selected from isocyanate compound and melamine amination Close the residue of at least one compound reaction of object.

Comprising having the conductive layer of the resin of the structure indicated by structural formula (1) to significantly improve electric conductivity.The present inventor pushes away Survey following reason.

Firstly, the present inventor speculates that the electric conductivity of conductive layer depends primarily on the movement of anion.It is fixed to the sun of resin Ionic organic group Z is hardly moved, and the anion for not being bonded to resin is easy movement.Furthermore, it appears that, the shifting of anion It is dynamic to be influenced by the electrostatic interaction with the Z with positive charge.In brief, if Z and anion have strong interaction, Anion is attracted to the Z for being fixed to resin to hardly move, and thus reduces the electric conductivity of conductive layer.On the contrary, if Z There is weak interaction with anion, then anion is hardly attracted to Z, and is easy movement, thus improves conductive layer Electric conductivity.

The present inventor speculates that advantageous effects of the invention (include the nitrogenous aromatic series of cationic by Z in structural formula (1) The cation matrix of heterocycle) type and be bonded to A₁And A₂Z in include the type of atom realize.The two will be described Parameter influences the detailed reason of the electric conductivity of conductive layer.

Firstly, the reason of by the species influence electric conductivity of describing Z.It is not comprising the nitrogenous heteroaromatic of cationic with Z Cation matrix (wherein Z is quaternary ammonium cation or pyrrolidines cation) the case where it is different, if Z is that nitrogenous aromatic series is miscellaneous Ring cationic organic group (such as glyoxaline cation or pyridylium), then due to being conjugated the positive electricity so that on nitrogen-atoms Lotus is distributed in other atoms on aromatic rings from nitrogen-atoms.Such distribution reduces the electrostatic interaction between Z and anion.It sees Come, it is mobile to improve electric conductivity that reduced electrostatic interaction is easy anion.

Second, it will now be described and be bonded to A₁And A₂Z in atom species influence conductive layer electric conductivity the reason of. Cation is by cation and can be fixed to resin with reacting for the compound of the cationoid reaction, thus one as resin Part introduces.In resin after the reaction, Z is via A₁And A₂It is bonded to the other parts (B of resin₁、B₂Be bonded to B₁And B₂'s Part).Via A₁And A₂It is bonded to the other parts (B of the resin of Z₁、B₂Be bonded to B₁And B₂Part) cause to be bonded to A₁ And A₂Z in atom around steric hindrance.

Cation on such as nitrogenous aromatic heterocyclic cation nitrogen-atoms with positive charge on nitrogen-atoms than in carbon or There is bigger positive charge density on hydrogen atom.For this purpose, the steric hindrance generated around nitrogen-atoms can prevent anion close to Z's Positive charge.As a result, anion is easy movement in the conductive layer to improve electric conductivity in the case where hardly being fettered by Z.

In contrast, if atomistic binding in Z in addition to nitrogen-atoms is to A₁And A₂, then there is lower positive charge density Atom (in addition to nitrogen-atoms) around generate steric hindrance, while there is the space around the nitrogen-atoms of higher positive charge density Steric hindrance reduces.For this purpose, anion is attracted to nitrogen-atoms to hardly move, the electric conductivity of conductive layer is thus reduced.

As described above, the interaction between Z and anion makes the positive charge on nitrogen-atoms by the aromatic character of Z It is distributed in both steric hindrances generated on other atoms and nitrogen-atoms with relatively high positive charge density and weakens.Knot Fruit, anion are easy movement in the case where not being attracted to Z, thus reduce the electric conductivity of conductive layer.

The ionic conductive agent for being used to form conductive layer has cation and anion.Cation has by structural formula (2) table The structure shown:

Wherein Z indicates the cation matrix comprising the nitrogenous heteroaromatic of cationic；A₁- H and A₂- H respectively indicates to be bonded To the substituent group of hydroxyl；A₁And A₂The nitrogen-atoms being respectively bonded in Z；And H is the hydrogen atom of hydroxyl.

Cation matrix can be any nitrogen atom heteroaromatic cation.The example includes imidazoles, pyrazoles (pyrazolium), pyridine and by these cation nitrogen-containing heterocycles and more than one aromatic ring condensation formed, Such as benzimidazole and quinoline condensed ring cation.The example includes such as oxazole (oxazolium), thiazole, benzo Oxazole and benzothiazole etc. optionally have the more than one heteroatomic cation in addition to nitrogen-atoms.In these sun In ion, the glyoxaline cation and pyridylium of the electric conductivity of relatively high conductive layer are preferably obtained.Cation Skeleton can have the more than one optional substituent group without hydroxyl (such as the alkyl with 1-30 carbon atom；As fluorine, The halogen groups such as chlorine, bromine and iodine；Such as methoxyl group and ethyoxyl alkoxy；Such as amide groups and cyano have heteroatomic substitution Base；And such as trifluoromethyl halogenated alkyl).

In the present invention, the substituent group for being bonded to hydroxyl includes alkyl or polyalkylene ether and hydroxyl, and the hydrogen of hydroxyl Atom is bonded to cation matrix via linking group.The alkyl being contained in the linking group of the oxygen atom with hydroxyl is such as Methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene and phenylene etc. have 1-30 carbon atom straight-chain or Cyclic annular, saturated or unsaturated alkyl, and can have more than one such as oxygen atom, nitrogen-atoms and the miscellaneous original of sulphur atom Son.Alkyl can also have the more than one substituent group without hydroxyl (such as the alkyl with 1-30 carbon atom；As fluorine, The halogen groups such as chlorine, bromine and iodine；Such as methoxyl group and ethyoxyl alkoxy；Such as amide groups and cyano have heteroatomic substitution Base；And such as trifluoromethyl halogenated alkyl).It is contained in linking group and includes polyalkylene ether group and hydroxyl The example of the oxyalkylene group of oxygen atom includes poly(ethylene glycol), poly- (propylene glycol) and poly- (tetramethylene glycol).

As research as a result, the inventors discovered that the hydrogen atom of hydroxyl to be connected to the linking group of cation matrix (A₁、A₂) from cation matrix to can have the length of 10 atoms below (from sun in the shortest distance of the hydrogen atom of hydroxyl 9 atoms below in cation matrix to the shortest distance of hydroxyl).For example, if A₁And A₂The oxygen of each free alkyl and hydroxyl Atomic building and alkyl are nonyl, then these linking groups have 9 in the shortest distance from cation matrix to hydroxyl Atom.That is, linking group in this case has the structure indicated by formula (V):

Wherein * indicates the binding site with the hydrogen atom of hydroxyl；* expression is bonded position with the nitrogen-atoms of cation matrix Point；And O indicates the oxygen atom of hydroxyl.

If A₁And A₂Respectively polytetramethylene glycol group and repeat number are 2, then these linking groups from sun from There are 9 atoms in sub- skeleton to the shortest distance of hydroxyl.

Wherein * indicates the binding site with the hydrogen atom of hydroxyl；* expression is bonded position with the nitrogen-atoms of cation matrix Point；And being bonded to the oxygen atom of * is the oxygen atom of hydroxyl.

Linking group in the shortest distance from cation matrix to hydroxyl with 9 atoms below improve by with The steric hindrance that the resin of hydroxyl reaction generates, so that anion is hardly close to cationic organic group.For this purpose, anion It is easy movement, obtains the conductive layer with high conductivity.

The example of the anion of ionic conductive agent includes fluosulfonic acid anion, fluorocarboxylic acid anion, fluorosulfonyl acyl Asia Amine anion, fluorosulfonyl methide anion, fluoroalkyl fluoboric acid anion, fluoroalkyl fluorophosphoric acid anion, halide Ion, carboxylate anion, sulfonic acid anion, tetrafluoro boric acid anion, hexafluorophosphoric acid anion, hexafluoroarsenate anion, hexafluoro Metaantimmonic acid anion, dicyanamide anion (dca), bis- (oxalic acid) acid anions, nitric acid anions and perchloric acid anion.

The example of fluosulfonic acid anion includes trifluoromethayl sulfonic acid anion, fluomethane sulfonic acid anion, perfluoro-ethyl Sulfonic acid anion, perfluoro propyl sulfonic acid anion, perfluoro butyl sulfonic acid anion, perfluoropentyl sulfonic acid anion, perfluoro hexyl Sulfonic acid anion and perfluoro octyl sulfonic acid anion.

The example of fluorocarboxylic acid anion include trifluoroacetic acid anion, perfluorinated acid anion, perfluorobutyric acid anion, Perfluor valeric acid anion and perfluor caproic acid anion.

The example of fluorosulfonyl imide anion includes three fluoro methane sulfonyl imide anions, perfluoro-ethyl sulphur Imide anion, perfluoro propyl sulfonyl imide anion, perfluoro butyl sulfonyl imide anion, perfluor penta Base sulfonyl imide anion, perfluoro hexyl sulfonyl imide anion, perfluorooctyl sulfonyl imide anion, fluorine Sulfonyl imide anion, and such as the cyclic annular anion such as bis- (sulfonyl) acid imides of ring-hexafluoropropane -1,3-.

The example of fluorosulfonyl methide anion includes trifluoromethane sulfonyl group methide anion, perfluoro-ethyl Sulfonyl methide anion, perfluoro propyl sulfonyl methide anion, perfluoro butyl sulfonyl methide yin from Son, perfluoropentyl sulfonyl methide anion, perfluoro hexyl sulfonyl methide anion and perfluorooctyl sulfonyl Methide anion.

The example of fluoroalkyl fluoboric acid anion includes three fluoboric acid of trifluoromethyl trifluoro acid anion and perfluoro-ethyl Anion.

The example of fluoroalkyl fluorophosphoric acid anion includes three-trifluoromethyls-trifluoro phosphate anion and three-perfluoro-ethyls- Trifluoro phosphate anion.

The example of halide ion includes fluoride ion, chloride ion, bromide ion and iodide ion.

The example of carboxylate anion includes such as acetate anion, propionic acid anion, butyric acid anion and caproic acid anion Alkyl carboxylic acid anion；And such as benzoic acid anion aromatic carboxylic acid anion.These anion can have selected from by More than one substituent group of group consisting of: the alkyl with 1-30 carbon atom, such as fluorine, chlorine, bromine and iodine halogen radical Group, such as methoxyl group and ethyoxyl alkoxy, such as amide groups and cyano contain heteroatomic substituent group, and such as trifluoromethyl Halogenated alkyl.

The example of sulfonic acid anion includes such as methylsulphur acid anion and ethanesulfonic acid anion alkyl sulfonic acid anion；And Such as benzene sulfonic acid and p-methyl benzenesulfonic acid anion aromatic sulphonic acid anion.These anion can be with selected from being made up of The more than one substituent group of group replaces: the alkyl with 1-30 carbon atom, such as fluorine, chlorine, bromine and iodine halogen group, such as first The alkoxies such as oxygroup and ethyoxyl, such as amide groups and cyano contain heteroatomic substituent group, and such as trifluoromethyl alkyl halide Base.

In these anion, for ionic conductive agent preferred anionic be fluosulfonic acid anion, fluorocarboxylic acid yin from Son, fluorosulfonyl imide anion, fluorosulfonyl methide anion, fluoroalkyl fluoboric acid anion, fluoroalkyl fluorine phosphorus Acid anion, tetrafluoro boric acid anion, hexafluorophosphoric acid anion, hexafluoroarsenate anion, hexafluoro-antimonic acid anion, cdicynanmide yin Ion and bis- (oxalic acid) acid anions, to obtain the electric conductivity of high conductive layer.

Ionic conductive agent can with relative to 100 mass parts conductive layers be 0.01 mass parts or more and 20 below the mass Amount cooperation.Amounts more than 0.01 mass parts can obtain the conductive layer with high conductivity.20 amount below the mass can obtain Obtain the conductive layer that ionic conductive agent hardly oozes out.

It can be with the compound of cationoid reaction

The compound with more than two functional groups reacted with hydroxyl can be indicated with the compound of cationoid reaction.Energy It is enough can not only be reacted with the cationic hydroxyl in ionic conductive agent with the compound of cationoid reaction and also can with it is aftermentioned The hydroxyl reaction for including in other compounds in polyalcohol and conductive layer.It can be with the example packet of the compound of cationoid reaction Include the isocyanate compound with isocyanate group；Epoxide compound with glycidyl；And there is alcoxyl The melamine compound of base, imino group and methylol.The example of isocyanate compound includes such as ethylidene diisocyanate With the aliphatic polyisocyantes such as 1,6- hexamethylene diisocyanate (HDI)；Such as isophorone diisocyanate (IPDI), ring The alicyclic polyisocyanates such as hexane -1,3- diisocyanate and hexamethylene -1,4- diisocyanate；As 2,4- toluene two is different Cyanate, 2,6- toluene di-isocyanate(TDI) (TDI), 4,4'- methyl diphenylene diisocyanate (MDI), the diphenylmethyl polymerizeing The aromatic isocyanates such as alkane diisocyanate, benzene dimethylene diisocyanate and naphthalene diisocyanate；And its copolymerization produces Object, isocyanuric acid ester products, TMP addition product and biuret and these block product.The example packet of epoxide compound Include such as 1,4- butanediol diglycidyl ether aliphatic diepoxide compounds compound；And such as bisphenol A diglycidyl ether Aromatic bicyclic oxide compound.The example of workable melamine compound includes methylated melamine, butylation Melamine, imino group melamine, methyl-butvl mixed type melamine and melamine methylol.

Among these compounds, such as toluene di-isocyanate(TDI), methyl diphenylene diisocyanate and the diphenylmethyl of polymerization The aromatic isocyanates such as alkane diisocyanate, as methylated melamine, butylated melamines, imino group melamine, The melamine compounds such as methyl-butvl mixed type melamine and melamine methylol are preferred.These compounds with The hydroxyl being contained in cation has high response, to reduce the ratio for not being bonded to the cation of resin.Such chemical combination Object can get the conductive layer that ionic conductive agent hardly oozes out.

The resin being contained in conductive layer may include the tree by that can synthesize with the compound of cationoid reaction and polyalcohol Rouge.Polyalcohol has multiple hydroxyls in the molecule, and hydroxyl and can react with the compound of cationoid reaction.Example packet It includes, but should be not limited to, the pure and mild polyester polyol of polyether polyols.The example of polyether polyol include polyethylene glycol, polypropylene glycol and Polytetramethylene glycol.The example of polyester polyol includes by such as 1,4- butanediol, 3- methyl-1,4- pentanediol and new penta 2 The diol components such as alcohol or such as three alkoxide component of trimethylolpropane with as adipic acid, phthalic anhydride, terephthalic acid (TPA) and The polyester polyol of the condensation reaction preparation of the dicarboxylic acids such as hexahydroxy phthalic acid.The pure and mild polyester polyol of these polyether polyols It when necessary can be in advance to have by such as 2,4 toluene diisocyanate (TDI), 1,4- methyl diphenylene diisocyanate (MDI) or the form of the prepolymer of the extended chain of isocyanates such as isophorone diisocyanate (IPDI) and formed.

Conductive layer can include the generation in addition to resin according to the present invention with the amount for not damaging advantageous effects of the invention Table resin, rubber material, compounding agent, conductive agent, conductive fillers, crosslinking agent and catalyst.Any resin can be added.Its Example includes epoxy resin, polyurethane resin, Lauxite, ester resin, amide resin, imide resin, amide imide tree Rouge, phenolic resin, vinylite, silicone resin and fluororesin.The example of rubber material includes Ethylene-Propylene-Diene copolymerization Rubber, nitrile rubber, neoprene, natural rubber, isoprene rubber, SBR styrene butadiene rubbers, silicon rubber, epichlorohydrin Rubber and polyurethane rubber.The example of compounding agent includes the filler for being generally used for resin, softening agent, processing auxiliary agent, tackifier, resists Stick and foaming agent.The example of conductive agent includes the fine grained of carbon black；Such as aluminium and copper conductive metal；And such as electric conductivity oxygen Change the conductive metal oxides such as zinc, conductive tin oxide and electric conductivity titanium oxide.The example of conductive fillers includes dioxy SiClx, quartz, titanium oxide and calcium carbonate.The example of crosslinking agent includes, but should be not limited to, tetraethoxysilane, di-t-butyl mistake Oxide, two (t-butyl peroxy) hexane of 2,5- dimethyl -2,5- and dicumyl peroxide.

If conductive layer according to the present invention is used as the superficial layer of electrophotography component and needs as superficial layer Fine grained can be added to conductive layer to control surface roughness by surface roughness.Especially it is used as the superficial layer of developer roll When, the fine grained for controlling surface roughness can have 3-20 μm of volume average particle size to obtain effective bearing developer Developer roll.Fine grained can be added to consolidating the amount that ingredient is 1-50 mass parts relative to the resin of 100 mass parts conductive layers Conductive layer, without damaging advantageous effects of the invention.Workable fine grained for controlling surface roughness is polyurethane tree Rouge, polyester resin, polyether resin, polyamide, acrylic resin and phenolic resin fine grained.

Conductive layer can be formed by any method.The example includes spray coating method, infusion process and the rolling method of coating.Day Present patent application special open S57-5047 describes the Dipcoat method by forming conductive layer from overflow coating at the top of dipping tank.This A little simple methods have high production stability.Conductive layer according to the present invention can be by known to electrophotography member arts Method be formed as elastic layer 3 shown in the A of Fig. 1.The example includes the method for being coextruded mandrel and conductive layer material； And by conductive layer formation fluent material injection include cylindrical pipe, the both ends of the pipe are set with keep mandrel bridge and The metal die of mandrel, and pass through the method for heating and making material solidification.

Electrophotography component according to the present invention can be used as such as charging member (roller), developer bearing member (development Roller), the electrophotographies component such as transfer member (roller) and cleaning blade.

If electrophotography component according to the present invention is used as the developer roll of developing apparatus, developer can be magnetism Or it is nonmagnetic, or can be monocomponent toner or double component developing.Developing apparatus can be non-contact type or contact Type.

Fig. 2 is the sectional view for showing handle box according to the present invention.It will be as the developer roll 16 of developer bearing member, aobvious Shadow scraper plate (toner control scraper plate) 21, electrophotographic photosensitive element 18, cleaning blade 26, useless toner container 25 and work Handle box 17 shown in Fig. 2 is integrally turned to for the charging roller 24 of charging member.Handle box is detachably mounted to electrofax figure Main body as forming equipment.Developing apparatus 22 includes toner container 20.Toner container 20 is filled with toner 15.It will toning Toner in agent container 20 is supplied by toner supplying roller 19 to the surface of developer roll 16, and is existed by developing blade 21 The toner layer with predetermined thickness is formed on the surface of developer roll 16.

Fig. 3 is to show including electrophotography component according to the present invention as developer roll 16 (as developer bearing member) Electronic photographing device sectional view.Electronic photographing device shown in Fig. 3 includes the developing apparatus 22 for being detachably mounted to it. Developing apparatus 22 includes that developer roll 16, toner supplying roller 19, the toner container 20 that can store toner 15 and development are scraped Plate 21.Electronic photographing device further includes the handle box 17 for being detachably mounted to it.Handle box 17 includes Electrifier frame, photoreceptor 18, cleaning Scraper plate 26, useless toner container 25 and charging roller 24.Only developing apparatus 22 can be detachably mounted to electrofax and set Standby or developing apparatus 22 and handle box 17 can be integrated and be detachably mounted to electronic photographing device.Selectively, It can be by developing apparatus 22, Electrifier frame, photoreceptor 18, cleaning blade 26, useless toner container 25 and the configuration of charging roller 24 in electricity The main body of sub- camera installation.That is, handle box according to the present invention can have as the charging roller 24 of charhing unit and as aobvious At least one of developer roll 16 of shadow unit, and the main body of electronic photographing device can be detachably mounted to.

Electrifier frame, photoreceptor 18 rotates in the direction of the arrow, and equal by charging roller 24 for charging Electrifier frame, photoreceptor 18 It charges evenly.By the laser beam 23 from the exposing unit for writing electrostatic latent image on Electrifier frame, photoreceptor 18 in Electrifier frame, photoreceptor Electrostatic latent image is formed on 18 surface.Developing apparatus 22 by contacting configuration with Electrifier frame, photoreceptor 18 supplies toner to electrostatic Sub-image, to make latent electrostatic image developing to be visualized as toner image.

Electrostatic latent image is set to carry out discharged-area development to make toner image develop on exposure portion.It will be on Electrifier frame, photoreceptor 18 Visualization toner image is transferred to the paper 34 as recording medium by the transfer roll 29 as transfer member.Paper 34 is passed through Paper feed roller 35 and the supply of adsorption roller 36 to equipment, and by it is cyclic annular transfer conveyer belt 32 Electrifier frame, photoreceptor 18 and transfer roll 29 it Between convey.Transfer conveyer belt 32 is driven by driven voller 33, driven roller 28 and jockey pulley 31.Voltage is applied from bias supply 30 Add to transfer roll 29 and adsorption roller 36.The paper 34 of toner image with transfer thereon is fixed by fixation facility 27, and It is discharged from equipment.Printing is completed.

It is non-transfer to be wiped off to the toner remained on Electrifier frame, photoreceptor 18 on paper 34 by cleaning blade 26, and store In useless toner container 25.

Developing apparatus 22 includes toner container 20 of the storage as the toner 15 of monocomponent toner, and along toning The opening portion configuration that the length direction of agent container 20 extends and the showing as developer bearing member towards Electrifier frame, photoreceptor 18 Shadow roller 16.Developing apparatus 22 makes the latent electrostatic image developing on Electrifier frame, photoreceptor 18 to visualize.Voltage is applied from bias supply 30 Add to developer roll 16 and developing blade 21.

Embodiment

Now, it will be described in wherein conductive layer according to the present invention and be used as the electrophotography structure as shown in the B of Fig. 1 The embodiment and comparative example of the superficial layer 4 of part 1, but the present invention is not limited to these embodiments.

(preparation of resilient roller D-1)

By priming paint (trade name, DY35-051；Can be obtained from Dow Corning Toray Silicone Co., Ltd.) it applies It is distributed in the metal core that the diameter made of SUS304 is 6mm and length is 278.9mm, and in the baking oven for being heated to 180 DEG C It bakes 20 minutes, to prepare mandrel.

Mandrel is put into metal die, and the addition-type silicon rubber composition containing following material is injected into metal die Die cavity in.

Liquid silicon rubber material (trade name, SE6724A/B；From Dow Corning Toray Silicone Co., Ltd. can obtain) 100 mass parts

Carbon black (trade name, TOKABLACK#4300；Can be obtained from Tokai Carbon Co., Ltd.) 15 mass parts

0.2 mass parts of SiO 2 powder as heat-resistant agent

0.1 mass parts of platinum catalyst

Then, metal die is heated to 150 DEG C 15 minutes, so that silicon rubber be made to solidify by vulcanization.From metal mold Removal has the mandrel of cure silicone rubber layer on circumferential surface in tool, and further heats at 180 DEG C 1 hour, to complete The curing reaction of silastic-layer.Preparation includes mandrel and the bullet for being formed in the silicon rubber elastic layer that the diameter of mandrel periphery is 12mm Property roller D-1.

(preparation of resilient roller D-2)

The surface for the stick that the length made of automatic steel is 252mm and outer diameter is 6mm is coated with by electroless Nickel.Then, by bonding agent be coated on from the both ends of stick remove 11mm range part entire stick (length of dispensing area: 230mm) to prepare mandrel.Melt bonding agent using conductive hot melt.With roll coater coating adhesive.

Then, following material is mixed with pressure kneader to prepare the rubber composition A of kneading with following amount.

NBR rubber (trade name: Nipol DN219；Can be obtained by ZEON Corporation) 100.0 mass parts

Carbon black (trade name: TOKABLACK#4300；Can be obtained by Tokai Carbon Co., Ltd.) 40.0 mass parts

Calcium carbonate (trade name: NANOX#30；Can be obtained by Maruo Calcium Co., Ltd.) 20.0 mass parts

Stearic acid (trade name: stearic acid S；Can be obtained by Kao Corporation) 1.0 mass parts,

In addition, mediate rubber composition A (166.0 mass parts) with the following material open roll for the amount being listed below Grinding machine is mixed to prepare unvulcanized rubber composition.

Sulphur (trade name: Sulfax 200S；Can be obtained by TSURUMI CHEMICAL INDUSTRY CO., LTD.) 1.2 Mass parts

Tetra-benzyl thiram disulfide (trade name: TBZTD；By Sanshin Chemical Industry Co., Ltd. can obtain) 4.5 mass parts

Then, the die head that internal diameter is 16.5mm is installed to the row of feed mechanism and unvulcanized rubber rollers with mandrel The cross-head extruder of mechanism out.The temperature of extruder and die head (crosshead) is adjusted to 80 DEG C and by conductive shaft core Conveying speed be adjusted to 60mm/sec.Under this condition, unvulcanized rubber composition is supplied with will be unvulcanized from extruder Rubber composition be coated in the conductive shaft core in crosshead, to form elastic layer.Then, mandrel is put into 170 DEG C Hot wind vulcanizing oven in, and heat 60 minutes.After cooling, the end of elastic layer, and the table of elastic layer are removed by cutting Face is ground with spinning mill, so that it is 8.4mm in that preparation, which is located at from the position diameter of central part towards each end 90mm of axis, Center portion diameter is the resilient roller D-2 of 8.5mm.

(preparation of superficial layer)

Now, description is used for the synthesis example for preparing superficial layer of the invention.

For ionic conductive agent of the invention can with for example, by via one it is more than the stage as Menschutkin react Precursor is prepared Deng known nucleophilic substitution, and carries out known ion-exchange reactions to prepare.

The example of workable nucleopilic reagent includes such as imidazolium compounds, pyridine compounds, pyrazole compound, oxazole chemical combination Object, thiazolium compounds, benzimidazole compound and quinoline compound etc. have the nucleophilic compound of nitrogen-atoms.

The example of workable electrophilic reagent includes the wherein substituted halogenated alkyl compounds of hydroxyl.

The example that can be used for the alkali metal salt of ion-exchange reactions includes such as fluoroalkyl sulfonic acids lithium and oroalkane sulfonyl base acyl The alkali metal salt of the anion containing aforementioned present invention such as imide.

Nucleopilic reagent and electrophilic reagent for nucleophilic substitution and the alkali metal salt for ion-exchange reactions It is expected that combination can obtain object ion conductive agent by the combination of known method.The synthesis that ionic conductive agent will now be described is real Example.Nucleopilic reagent and electrophilic reagent and alkali metal salt for ion-exchange reactions are shown in table 1,2 and 9.

(synthesis of ionic conductive agent precursor P-1)

By blender and tetrahydrofuran (hereinafter referred to as THF can be obtained from KANTO CHEMICAL CO., INC.) (50ml) It is put into the eggplant type flask configured with dimroth's condenser.Sodium hydride (can be obtained) from KANTO CHEMICAL CO., INC. (12.5g, 0.52mol) dispersion, and eggplant type flask is cooling in ice bath.By nucleopilic reagent N-1 (imidazoles, from Tokyo Chemical Industry Co., Ltd. can obtain) (8.94g, 0.13mol) be dissolved in THF (50ml) to prepare solution, and It waits a moment and solution is added dropwise slowly.Ice bath is removed, and solution is stirred at room temperature 2 hours.Electrophilic reagent Q-1 is added at room temperature (ethylene bromohyrin can be obtained from Tokyo Chemical Industry Co., Ltd.) (41.1g, 0.33mmol), and make solution It is heated to reflux at 70 DEG C 7 hours.After reaction, reaction solution is filtered, and washes off insoluble component with THF.It steams under reduced pressure Solvent in filtrate.Product is re-dissolved in methylene chloride, and solution is filtered.After recycling filtrate, steam under reduced pressure Solvent.Condensation product is washed with diethyl ether, and is dried under reduced pressure, to prepare ionic conductive agent precursor P-1 (28g).

Table 1

Table 2

(synthesis of ionic conductive agent precursor P-2, P-7 and P-16)

In addition to will be used as raw material nucleopilic reagent and electrophilic reagent type and use level change as shown in table 3 other than, Ionic conductive agent precursor P-2, P-7 and P-16 are prepared in a manner of identical with the synthesis of ionic conductive agent precursor P-1.

Table 3

(synthesis of ionic conductive agent precursor P-3)

By nucleopilic reagent N-1 (imidazoles can be obtained from Tokyo Chemical Industry Co., Ltd.) (6.17g, 0.09mol), electrophilic reagent Q-2 (2- [2- (2- chloroethoxy) ethyoxyl] ethyl alcohol, from Tokyo Chemical Industry Co., Ltd. can obtain) (23g, 0.14mol), potassium carbonate (can be obtained from KANTO CHEMICAL CO., INC.) (25g, 0.18mol) and acetone (200ml) is put into the flask configured with dimroth's condenser, and heats solution at 65 DEG C It is refluxed overnight.After reaction, reaction solution is filtered, and steams the solvent in filtrate under reduced pressure.Pass through silica gel column chromatography (second Acetoacetic ester) make product purification to prepare the compound of (tertiarized) nucleopilic reagent containing tertiary amine.Then compound is molten Solution adds electrophilic reagent Q-4 (the bromo- n-butyl alcohol of 4-, from Tokyo Chemical in methylene chloride (50ml) Industry Co., Ltd. can obtain) (20.8g, 0.14mol).Solution is heated to reflux 18 hours at 40 DEG C.After reaction, Solvent is steamed under decompression.Product is washed with diethyl ether, and dry to prepare as the quaternized of white powder (quaternarized) ionic conductive agent precursor P-3.

(synthesis of ionic conductive agent precursor P-4, P-5 and P-6)

In addition to will be used as raw material nucleopilic reagent and electrophilic reagent type and use level change as shown in table 4 other than, Ionic conductive agent precursor P-4, P-5 and P-6 are prepared in a manner of identical with the synthesis of ionic conductive agent precursor P-3.

Table 4

(synthesis of ionic conductive agent precursor P-8)

Distilled THF (500ml) and 2,6 di tert butyl pyridine (can be obtained) (1g) to be put into from Sigma Aldrich In round-bottomed flask, and it is cooled to 0 DEG C in a nitrogen atmosphere.Then, addition methyl trifluoro methanesulfonates is (from Tokyo Chemical Industry Co., Ltd. can obtain) (3.6g, 22mmol) be used as initiator.Add nucleopilic reagent N-3 (2- methyl Benzimidazole can be obtained from Tokyo Chemical Industry Co., Ltd.) (5.87g, 44.5mmol) with terminate polymerization, and And by polymer in water with precipitating in diethyl ether to refine.Polymer is dried under reduced pressure, to prepare as white powder The imidazoles replaced by tetramethylene glycol at end.In order to keep the white powder quaternized, methylene chloride is dissolved the polymer in In (200ml), and add electrophilic reagent Q-3 (the bromo- 1- hexanol of 6-, from Tokyo Chemical Industry Co., Ltd. can obtain) (12.1g, 67mmol).Solution is heated to reflux 18 hours at 40 DEG C.After reaction, solvent is steamed under reduced pressure. Product is washed with diethyl ether, and dry to prepare white powder.In order to be chloride ion by anion exchange, will polymerize Object have disperse ion exchange resin Dowex therein (can from Wako Pure Chemical Industries, Ltd. ) methanol in stir 2-3 hours.Ion exchange resin is removed by filtering, and dry to prepare quaternized ion Conductive agent precursor P-8.The anion of P-8 is chloride ion.

(synthesis of ionic conductive agent precursor P-9)

In addition to by nucleopilic reagent N-1 (imidazoles can be obtained from Tokyo Chemical Industry Co., Ltd.) (2.87g, 42mmol), (the bromo- DODECANOL, 1- of 12-, can from Tokyo Chemical Industry Co., Ltd. by electrophilic reagent Q-8 ) (16.8g, 63mmol) for react other than, prepare ionic conductive agent in a manner of identical with ionic conductive agent precursor P-8 Precursor P-9.

(synthesis of ionic conductive agent precursor P-10)

By nucleopilic reagent N-4 (2- pyridine ethanol can be obtained from Tokyo Chemical Industry Co., Ltd.) (12.0g, 0.15mol) is dissolved in methylene chloride (200ml), and add electrophilic reagent Q-1 (2- bromoethanol, from Tokyo Chemical Industry Co., Ltd. can obtain) (38g, 0.3mol).It is small that solution is heated to reflux 18 at 40 DEG C When.After reaction, solvent is steamed under reduced pressure.Diethyl ether is used to wash the quaternized ion to prepare as white powder product Conductive agent precursor P-10.

(synthesis of ionic conductive agent precursor P-11, P-12, P-14)

It is as shown in table 5 as the nucleopilic reagent of raw material and the type of electrophilic reagent and use level in addition to will be used to react Other than change, ionic conductive agent precursor P-11, P-12 and P-14 are prepared in a manner of identical with ionic conductive agent precursor P-10.

Table 5

(synthesis of ionic conductive agent precursor P-13)

Distilled THF (500ml) and 2,6- di-t-butyl pyridine (can be obtained) (1.2g) to put from Sigma Aldrich Enter in round-bottomed flask, and is cooled to 0 DEG C under an inert atmosphere.Then, Methyl triflate (4.92g, 30mmol) is added As initiator.It adds nucleopilic reagent N-4 (2- pyridine ethanol can be obtained from Tokyo Chemical Industry Co., Ltd.) (7.3g, 59mmol) is to terminate polymerization.By polymer in water with precipitating in diethyl ether to refine, and it is dried under reduced pressure, To prepare the pyridiniujm replaced by tetramethylene glycol as white powder.In order to by anion exchange be chloride from Son, by polymer have disperse ion exchange resin Dowex therein (from Wako Pure Chemical Industries, Ltd. can obtain) methanol in stir 2-3 hours.Ion exchange resin is removed by filtering, and drying is quaternized to prepare Ionic conductive agent precursor P-13.The anion of P-13 is chloride ion.

(synthesis of ionic conductive agent precursor P-15)

By tert-butyldimethylsilyl chloride compound and electrophilic reagent Q-6 (the bromo- 1- decyl alcohol of 10-, from Tokyo Chemical Industry Co., Ltd. can obtain) (19g, 80mmol) in n,N-Dimethylformamide, in the presence of imidazoles Under, at room temperature react 3 hours.By product liquid separation in ethyl acetate/water, and it is dry with prepare wherein hydroxyl by monosilane The compound that base replaces.By nucleopilic reagent N-7 (3- bromopyridine can be obtained from Tokyo Chemical Industry Co., Ltd.) (8.55g, 54mmol) is dissolved under an inert atmosphere in distilled THF (400ml), and will be molten in dry ice/methanol bath Liquid is cooled to -78 DEG C.Then, be slowly added dropwise 2.6mol/l n-BuLi/hexane solution (from KANTO CHEMICAL CO., INC. can obtain) (23ml, 60mmol), and stir 30 minutes.Then, silylated Q-6 is slowly added dropwise in THF Solution (50ml).After solution is reacted 3 hours at -78 DEG C and is stayed overnight at room temperature, hydrochloric acid is added in reaction solution, and 1 hour is stirred at room temperature with desilylation.After steaming solvent under reduced pressure, by product methylene chloride/water liquid separation, and Dry 3- (10- hydroxydecyl) pyridine to prepare as white powder.The powder is dissolved in methylene chloride (50ml), And adding electrophilic reagent Q-8, (the bromo- DODECANOL, 1- of 12-, can from Tokyo Chemical Industry Co., Ltd. ) (15.8g, 60mmol) with quaternized.Solution is heated to reflux 18 hours at 40 DEG C.After reaction, steam under reduced pressure molten Agent.Product is washed with diethyl ether, and the dry quaternized ionic conductive agent precursor P-15 to prepare as white powder.P- 15 anion is bromide ion.

(synthesis of ionic conductive agent precursor P-17, P-18 and P-19)

Other than in addition to the nucleopilic reagent that will be used to react and electrophilic reagent changes as shown in table 6, with ionic conductive agent The identical mode of precursor P-15 prepares ionic conductive agent precursor P-17, P-18 and P-19.

Table 6

(synthesis of ionic conductive agent precursor P-20)

Dimroth's condenser is installed to eggplant type flask.By nucleopilic reagent N-12 (dibutyl amine, from Tokyo Chemical Industry Co., Ltd. can obtain) (14.5g, 0.11mol) and electrophilic reagent Q-1 (ethylene bromohyrin, from Tokyo Chemical Industry Co., Ltd. can obtain) (35.5g, 0.28mol) is dissolved in acetonitrile (200ml), and adds carbon Sour potassium (69g, 0.5mol).Solution is refluxed overnight under 90 DEG C of boiling point.By reaction solution ethyl acetate/moisture liquid to recycle Organic layer.Solvent is steamed under reduced pressure to prepare the quaternized ionic conductive agent precursor P-20 as white solid.Precursor Anion be bromide ion.

(synthesis of ionic conductive agent precursor P-21, P-22 and P-23)

Other than in addition to the nucleopilic reagent that will be used to react and electrophilic reagent changes as shown in table 7, with ionic conductive agent The identical mode of precursor P-20 prepares ionic conductive agent precursor P-21, P-22 and P-23.

Table 7

(synthesis of ionic conductive agent precursor P-24)

It adds nucleopilic reagent N-16 (4,5- dibromo imidazoles, can be obtained from Sigma Aldrich) (15.5g, 73mmol), it is electrophilic Sub- reagent Q-12 (1- bromobutane can be obtained from Tokyo Chemical Industry Co., Ltd.) (15.2g, 0.11mol), Potassium carbonate (can obtain) (27.8g, 0.2mol) and acetone (100ml) from KANTO CHEMICAL CO., INC., and at 65 DEG C Heated overnight at reflux.After reaction, reaction solution is filtered.The solvent in filtrate is steamed under reduced pressure, and passes through silica gel column chromatography Method (ethyl acetate) makes product purification to prepare the compound of the nucleopilic reagent with tertiary amine.Then, compound is dissolved in In methylene chloride (50ml).Add electrophilic reagent Q-11 (iodoethane, from Tokyo Chemical Industry Co., Ltd. Can obtain) (17.1g, 0.11mmol), and solution is heated to reflux 18 hours at 40 DEG C.After reaction, steam under reduced pressure molten Agent.Diethyl ether is used to wash the 4,5- dibromoethyl butyl imidazole iodide to prepare as white powder product.Then, will Compound is dissolved in a nitrogen atmosphere in distilled THF (300ml), and solution is cooled in dry ice/methanol bath- 78℃.Then, n-BuLi/hexane solution (can obtain from KANTO CHEMICAL CO., INC.) of 2.6M is slowly added dropwise (80ml), and stir 30 minutes.Then, slowly be added dropwise nucleopilic reagent Q-9 (2- bromine oxethyl-t-butyldimethyl silane, from Sigma Aldrich can be obtained) solution (100ml) of (52.3g, 0.22mmol) in THF.It is small that solution is reacted to 3 at -78 DEG C When and at room temperature overnight after, hydrochloric acid is added in reaction solution, and be stirred at room temperature 1 hour with desilylation. After steaming solvent under reduced pressure, by product ionic conductive agent precursor of the ethyl acetate/moisture liquid to prepare as white powder P-24.The anion of P-24 is iodide ion.

(synthesis of ionic conductive agent precursor P-25, P-26, P-27 and P-28)

Other than in addition to the nucleopilic reagent that will be used to react and electrophilic reagent changes as shown in table 8, with ionic conductive agent The identical mode of precursor P-24 prepares ionic conductive agent precursor P-25, P-26, P-27 and P-28.Ionic conductive agent precursor P-24's Q-12 in synthesis indicates electrophilic reagent A, Q-11 electrophilic reagent B and Q-9 electrophilic reagent C.

Table 8

The anion of the ionic conductive agent precursor P-1 to P-28 prepared by the above method is such as chloride ion and bromination The halide ions such as object ion.In order to be desired anion by these anion exchanges, prepared by following ion-exchange reactions Object ion conductive agent.The anion exchange salt used is listed in Table 9 below.

(synthesis of ionic conductive agent C-1)

Ionic conductive agent precursor P-1 (7.7g, 33mmol) is dissolved in methylene chloride (50ml).Add anion exchange Salt A-1 (bis- (trifluoromethyl sulfonyl) imide lis (bis (trifluoromethane sulfone) imidelithium), Can be obtained from Tokyo Chemical Industry Co., Ltd.) aqueous solution of (10.3g, 36mmol), and it is small to stir 24 When.By solution liquid separation to obtain organic layer.By organic layer with moisture liquid 2 times, and methylene chloride is steamed under reduced pressure, to make The standby ionic conductive agent C-1 with bis- (trifluoromethyl sulfonyl) imide anions.

Table 9

(synthesis of ionic conductive agent C-2 to C-11, C-13 to C-30)

In addition to the type and use level such as table 10 of ionic conductive agent precursor and anionic ion the exchange salt that will be used to react Other than shown change, ionic conductive agent C-2 to C-11 and C-13 are prepared in a manner of identical with ionic conductive agent C-1 to C-30. For ionic conductive agent C-12, ionic conductive agent precursor P-11 is used as former state and without ion exchange.

Table 10

The structure of ionic conductive agent C-1 to C-8, C-10 and C-26 to C-28 is indicated by structural formula (3) and is shown in table 11 In, the structure of ionic conductive agent C-11 to C-17, C-29 and C-30 is indicated by structural formula (4) and is shown in table 12, and from The structure of subconductivity agent C-9 and C-18 to C-25 is indicated by structural formula (5)-(13).

Table 11

Table 12

In structural formula (5), n 2.

(synthesis of isocyanate-terminated prepolymer B-1)

In a nitrogen atmosphere, while the internal temperature of reaction vessel is maintained at 65 DEG C, by polyalcohol F-1 (poly- (four Methylene glycol) (trade name: PTMG2000；Can be obtained from Mitsubishi Chemical Corporation)) (100 mass Part) be gradually added dropwise in reaction vessel isocyanates D-1 polymerization MDI (trade name: Millionate MR200；From Tosoh Corporation (Nippon Polyurethane Industry Co., Ltd. before) can be obtained) (38 mass parts) In.After being added dropwise to complete, carry out reaction 2 hours at 65 DEG C.Reaction mixture is cooled to room temperature, and uses methyl ethyl ketone (MEK) (50 mass parts) dilution with prepare isocyanate-terminated prepolymer B-1 solution (isocyanate group content: 3.4%).

(synthesis of isocyanate-terminated prepolymer B-2 to B-4)

Other than the type and use level of the isocyanates and polyalcohol that will be used to react change as shown in table 13-15, Isocyanate-terminated prepolymer B-2 to B-4 is prepared in a manner of identical with isocyanate-terminated prepolymer B-1.

Table 13

Table 14

Table 15

(embodiment 1)

Now, the manufacturing method of electrophotography component according to the present invention will be described.

Following material is mixed to prepare superficial layer material by stirring.

Reactive compounds

Isocyanate-terminated 66.4 mass parts of prepolymer B-1

Polyalcohol

Polyol E -1 (poly- (tetramethylene glycol) (can be obtained from Mitsubishi Chemical Corporation)) 30.6 mass parts

Ionic conductive agent

3.0 mass parts of ionic conductive agent C-1

Polyurethane resin fine grained (trade name, Art-pearl C-400；From Negami Chemical Industrial Co., Ltd. can be obtained) 90.0 mass parts

Then, methyl ethyl ketone (hereinafter referred to as MEK) is added to the mixture, so that always ingredient is 30 mass % admittedly In, and mixed with sand mill.With MEK by the viscosity-adjusting agent of mixture to 10-13cps, formed to prepare superficial layer with painting Material.

The resilient roller D-1 of above-mentioned preparation is impregnated in superficial layer formation coating in the elastic layer of resilient roller D-1 The film of coating is formed on surface.By dried coating film.And film is further heated to 1 hour at 160 DEG C in elastic layer Periphery formed with a thickness of 15 μm of superficial layer.The electrophotography component of embodiment 1 is made.

The structure indicated by structural formula 1 for including in resin in superficial layer can be for example, by pyrolysis GC/MS, releasing Gas analysis (EGA-MS) or FT-IR or NMR analysis are to confirm.

The superficial layer of embodiment 1 with pyrolysis plant (trade name: Pyrofoil Sampler JPS-700, from Japan Analytical Industry Co., Ltd. can obtain) and GC/MS equipment (trade name: Focus GC/ISQ, from Thermo Fisher Scientific Inc. can be obtained), under 590 DEG C of pyrolysis temperature use helium as carrier gas to analyze.From obtaining Fragment peak, confirm that the resin that is contained in superficial layer has the structure indicated by structural formula (1).

Thus electrophotography component that embodiment 1 is prepared evaluates following item as developer roll (developer bearing member) Mesh.

[measurement of the current value of developer roll]

Developer roll is placed 6 hours or more in 23 DEG C of environment with 45%RH (hereinafter referred to as N/N), and in N/N ring The current value of developer roll is measured under border.

The B of the A and Fig. 4 of Fig. 4 show the schematic configuration of the fixture of the evaluation for developer roll current value.Conductive layer Electric conductivity higher (resistance is smaller) cause the current value flowed through in developer roll bigger.For this purpose, perseverance can be being applied by measurement The current value flowed through in developer roll during constant voltage evaluates the electric conductivity of conductive layer.

Firstly, in the A of Fig. 4, via electric conductivity bearing 38 by the load applying of 4.9N to electrophotography component 1 Conductive shaft core 2 both ends while, so that the cylindrical metal 37 of diameter 40mm is rotated and make electricity as developer roll Sub- photograph component 1 follows the rotation of cylindrical metal 37 to rotate with 60rpm.

Then, in the B of Fig. 4, by high voltage power supply 39 apply 50V voltage, and measure cylindrical metal 37 with The current potential between the resistor both ends with known resistance (more than double figures lower than the resistance of developer roll) configured between ground Difference.Potential difference voltmeter 40 (can be obtained from Fluke Corporation, 189 TRUE RMS MULTIMETER) measurement.By electricity The resistance of potential difference and resistor calculates the electric current flowed via the electrophotography component 1 as developer roll in cylindrical metal. Potential difference samples 3 seconds after applying voltage 2 seconds, and the electric current for developer roll being defined as by the value of the mean value calculation sampled Value.

[evaluation of ghost image]

Then, by as described above the developer roll of measured in advance current value in 15 DEG C of temperature and 10% relative humidity It places 6 hours or more in the environment of (hereinafter referred to as L/L), and is evaluated by following steps.

By with construction shown in Fig. 3 as electronic photographing device laser printer (trade name: LBP7700C, from Canon Inc. can be obtained) it is placed in L/L environment.Using the electrophotography component prepared in embodiment as developer roll install to Printer is to evaluate ghost image.

When evaluating ghost image, black toner is used.In the black of the front end of A4 size paper printing 15mm × 15mm Then solid image prints half tone image in the remainder of paper.Then, it is visually commented according to the benchmark of following ghost image evaluation Valence correspond to the swing circle of developer roll and in the printing paper that occurs half tone image part uneven concentration.

(evaluation criteria of ghost image under L/L environment)

A: ghost image is not found

B: ghost image is found very slightly

C: ghost image is slightly found

D: ghost image is found significantly

(embodiment 8)

Now, the manufacturing method of another electrophotography component according to the present invention will be described.

Following material is mixed to prepare superficial layer material by stirring.

Reactive compounds

(bisphenol A diglycidyl ether is (from Tokyo Chemical Industry Co., Ltd. by reactive compounds R-2 Can obtain)) 18.0 mass parts

Polyalcohol

Polyol E -4 (polyethylene glycol (can be obtained from Sanyo Chemical Industries, Ltd.)) 72.0 mass parts

Ionic conductive agent

10.0 mass parts of ionic conductive agent C-8

Then, methyl ethyl ketone (hereinafter referred to as MEK) is added in the mixture, so that always ingredient is 30 matter admittedly % is measured, and is mixed with sand mill.The viscosity-adjusting agent of mixture to 10-13cps is prepared to superficial layer with MEK to be formed with painting Material.

The resilient roller D-1 of above-mentioned preparation is impregnated in superficial layer formation coating in the elastic layer of resilient roller D-1 The film of coating is formed on surface.By dried coating film.Film is further heated to 2 hours at 180 DEG C in the outer of elastic layer The superficial layer that week is formed with a thickness of 15 μm.The electrophotography component of embodiment 8 is made.

(embodiment 9)

Following material is mixed to prepare superficial layer material by stirring.

Reactive compounds

(2,4,6- tri- [bis- (methoxy) amino] -1,3,5- triazine is (from Tokyo by reactive compounds R-3 Chemical Industry Co., Ltd. can be obtained)) 15.0 mass parts

Polyalcohol

Polyol E -4 (polyethylene glycol (can be obtained from Sanyo Chemical Industries, Ltd.)) 82.0 mass parts

Ionic conductive agent

3.0 mass parts of ionic conductive agent C-9

The resilient roller D-1 of above-mentioned preparation is impregnated in superficial layer formation coating in the elastic layer of resilient roller D-1 The film of coating is formed on surface.By dried coating film.Film is further heated to 20 minutes at 180 DEG C in the outer of elastic layer The superficial layer that week is formed with a thickness of 15 μm.The electrophotography component of embodiment 9 is made.

(embodiment 2-7,10-21)

In addition to by the superficial layer material of embodiment 1, that is, reactive compounds, polyalcohol and ionic conductive agent such as table 16- Other than changing shown in 18, superficial layer formation coating is prepared in the same manner as example 1.Using with embodiment 1,8 and 9 phases Polyurethane resin fine grained (trade name, the Art-pearl C-400 of same amount；From Negami Chemical Industrial Co., Ltd. can be obtained) (90.0 mass parts).Coating is respectively applied in the same manner as example 1 and is distributed in resilient roller D-1, does It is dry and heat, to prepare the electrophotography component of embodiment 2-7 and 10-21.

Table 16

Table 17

Table 18

(comparative example 1)

As superficial layer material, that is, by ionic conductive agent C-22 (3.0 mass parts), isocyanate-terminated pre-polymerization Object B-1 (67.0 mass parts) and polyurethane resin fine grained (trade name, Art-pearl C-400；From Negami Chemical Industrial Co., Ltd. can obtain) (90.0 mass parts) by stirring with polyol E -1 (poly- (tetramethylene glycol), from Mitsubishi Chemical Corporation can be obtained) (30.0 mass parts) mixing.

In addition to this, superficial layer formation coating is prepared in the same manner as example 1 to prepare the surface of comparative example 1 Layer forms and uses coating.Superficial layer formation is coated on to the silicon rubber bullet of resilient roller D-1 with coating in the same manner as example 1 Property the surface of layer and dry to form superficial layer.Prepare the electrophotography component of comparative example 1.

(comparative example 2-9)

In addition to by the superficial layer material of embodiment 1, that is, the reactive chemical combination of the superficial layer material as embodiment 1 Other than object, polyalcohol and ionic conductive agent change as shown in table 19, superficial layer is prepared in the same manner as example 1 and forms use Coating.Use polyurethane resin fine grained (trade name, the Art-pearl C-400 of amount same as Example 1；From Negami Chemical Industrial Co., Ltd. can be obtained) (90.0 mass parts).It is in the same manner as example 1 that coating is each From being coated on resilient roller, drying and heat.To prepare the electrophotography component of comparative example 2-9.

Table 19

In embodiment 1-21 and comparative example 1-9 to the current value of developer roll and the evaluation result of ghost image and resin and yin The composition of ion is shown in table 20.

The electrophotography component of embodiment 1-21 including the superficial layer comprising resin according to the present invention obtains Gao Pin Matter image.

In particular, being bonded in the resin of embodiment 1-5,8,9,11,12,14 and 18-21 included in ionic conductive agent Cation in hydroxyl alkylene oxide structure of the substituent group with terminal hydroxyl and with 2-8 carbon atom.Including including root Electrophotography component according to the superficial layer of resin of the present invention has high conductivity to obtain high quality image.

In addition, the resin in embodiment 1-5,8,9,11,12 and 14 includes that its cation has glyoxaline structure and pyridine The ionic conductive agent of one of structure.Electrophotography component including the superficial layer comprising this kind of resin has extra high lead Electrically to obtain high quality image.

In contrast, the resin of comparative example 1-4 does not have the nitrogenous aromatic heterocyclic cation in ionic conductive agent, therefore Electrophotography component comprising this kind of resin has low electric conductivity, leads to image deflects.

The resin of comparative example 5-9, substituent group that is including in the cation of ionic conductive agent and being bonded to hydroxyl with except sun Atom other than the nitrogen-atoms of the nitrogenous heteroaromatic of ion combines.Nitrogenous aromatic series in comparative example 5-7, in cation Heterocycle has more than two nitrogen-atoms, and one or two of two substituent groups for being bonded to hydroxyl are not bonded to nitrogen original Son.In comparative example 8 to 9, the nitrogenous heteroaromatic in cation only has a nitrogen-atoms, and two for being bonded to hydroxyl take Dai Ji is not bonded to nitrogen-atoms.For this purpose, the electrophotography component comprising this kind of resin has low electric conductivity, image is caused to lack It falls into.

(embodiment 22)

Superficial layer formation coating is prepared in the same manner as example 1.In addition to replacing resilient roller D- with resilient roller D-2 Other than 1, superficial layer formation is coated and dried and is heated with coating in the same manner as example 1.Prepare the electricity of embodiment 22 Component is used in son photograph.

(comparative example 10)

Other than the material of comparative example 1 is used as superficial layer material, ratio is prepared in a manner of identical with embodiment 22 Compared with the electrophotography component of example 10.

The electrophotography component of embodiment 22 and comparative example 10 is used as charging member (charging roller) to evaluate following items.

[current value of charging roller]

It will be placed 6 hours or more under N/N environment as the electrophotography component of charging roller, and under N/N environment Measure the current value of charging roller.

The B of the A and Fig. 4 of Fig. 4 show the schematic configuration of the fixture of the current value for evaluating charging roller.

As shown in the A of Fig. 4, the loading of 4.9N is being applied to the electronics photograph as charging roller via electric conductivity bearing 38 While mutually with the both ends of the conductive shaft core 2 of component 1, make the cylindrical metal 37 of diameter 30mm rotated with 30rpm and The electrophotography component 1 as charging roller is set to follow the rotation of cylindrical metal 37 and rotate.

Then, in the B of Fig. 4, by high voltage power supply 39 apply 200V voltage, and measure cylindrical metal 37 with Between the both ends of resistor being configured between ground and with known resistance (more than double figures lower than the resistance of charging roller) Potential difference.Current potential is measured with voltmeter 40 (can obtain from Fluke Corporation, 189 TRUE RMS MULTIMETER) Difference.By the resistance of potential difference and resistor, calculating is flowed in cylindrical metal via the electrophotography component 1 as charging roller Dynamic electric current.Potential difference samples 3 seconds after applying voltage 2 seconds, and the value calculated by sample mean is defined as developer roll Current value.

[evaluation of the image with horizontal stripe]

The low electric conductivity of charging roller can behave as the uneven concentration (horizontal stripe) of the half tone image of fine streaks.It is such Image is known as the image with horizontal stripe.The electric conductivity the low more may cause such image with horizontal stripe.

By each self installation of electrophotography component as charging roller prepared in embodiment to being used as electronic photographing device Laser printer (trade name: LBP7700C can be obtained from Canon Inc.).Half tone image is exported (respectively along Electrifier frame, photoreceptor Direction of rotation and direction of rotation vertical direction respectively have width be 1 point and be divided into 2 points line image).Visually observation The image of printing is to evaluate the uneven concentration (horizontal stripe) occurred with fine streaks.Evaluation result is shown in table 21.According to Following benchmark evaluation horizontal stripe.

A: horizontal stripe is not generated.

B: only image end slightly generates horizontal stripe

C: almost half image significantly generates horizontal stripe.

Table 21

The electrophotography component of embodiment 22 including the superficial layer comprising resin according to the present invention has highly conductive Property to obtaining high quality image.

In contrast, the resin of comparative example 10 does not have the nitrogenous aromatic heterocyclic cation in ionic conductive agent, therefore Electrophotography component comprising this kind of resin has low electric conductivity, leads to image deflects.

Although the present invention has been described in reference example embodiment, it should be understood that showing the invention is not limited to disclosed Example property embodiment.The range of claims meets broadest explanation to cover all such improvement and equivalent structure And function.

Claims

1. a kind of electrophotography component (16；24) comprising conductive shaft core (2) and conductive layer (3；4；5),

It is characterized in that, the conductive layer (3；4；5) comprising resin and anion with the structure indicated by structural formula (1):

Wherein Z indicates the cation matrix comprising the nitrogenous heteroaromatic of cationic；A₁And A₂Each independently represent linker The nitrogen-atoms of group and the nitrogenous heteroaromatic of the cationic being bonded in Z,

Condition is,

When the nitrogenous heteroaromatic of the cationic only has a nitrogen-atoms, A₁And A₂One of be bonded to the nitrogen-atoms, And A₁And A₂Another be bonded to the carbon atom in the nitrogenous heteroaromatic of the cationic,

And when the nitrogenous heteroaromatic of the cationic has more than two nitrogen-atoms, A₁And A₂Be bonded to it is described sun from Two nitrogen-atoms in the sub- nitrogenous heteroaromatic of property；And

B₁And B₂Each independently represent hydroxyl hydrogen atom and can be anti-with the compound of the atomic reaction of hydrogen of the hydroxyl The residue answered.

2. electrophotography component (16 according to claim 1；24), wherein the linking group has oxyalkylene knot Structure.

3. electrophotography component (16 according to claim 2；24), wherein the alkylene oxide structure is by formula (III) Or the structure that (IV) is indicated:

Wherein * * * indicates the binding site with the residue；* * * indicates the binding site with the nitrogen-atoms；C be 1 or more and 9 integers below；And d is 1 or more and 4 integers below.

4. electrophotography component (16 according to claim 1；24), wherein the Z in the structural formula (1) includes being selected from At least one of cationic imidazole skeleton and cationic pyridine skeleton skeleton.

5. electrophotography component (16 according to claim 1；24), wherein the anion be it is selected from the following at least A kind of anion: fluosulfonic acid anion, fluorocarboxylic acid anion, fluorosulfonyl imide anion, fluorosulfonyl methide Anion, fluoroalkyl fluoboric acid anion, fluoroalkyl fluorophosphoric acid anion, tetrafluoro boric acid anion, hexafluorophosphoric acid anion, six Fluorine arsenic acid anion, hexafluoro-antimonic acid anion, dicyanamide anion (dca) and bis- (oxalic acid) acid anions.

6. electrophotography component (16 according to claim 1；24), wherein B in the structural formula (1)₁Or B₂Include The hydrogen atom of hydroxyl is changed with selected from least one of isocyanate compound, epoxide compound and melamine compound Close the residue of object reaction.

7. electrophotography component (16 according to claim 1；24), wherein

The resin is by nitrogenous aromatic heterocyclic cation and the chemical combination that can be reacted with the nitrogenous aromatic heterocyclic cation Object synthesis,

There are two the substituent groups for being bonded to hydroxyl for the nitrogenous aromatic heterocyclic cation tool, and

When the nitrogenous heteroaromatic in the nitrogenous aromatic heterocyclic cation only has a nitrogen-atoms, a substituent group It is bonded to the nitrogen-atoms, and another substituent group is bonded to the carbon atom of the nitrogenous heteroaromatic, and

When the nitrogenous heteroaromatic in the nitrogenous aromatic heterocyclic cation has more than two nitrogen-atoms, substituent group Two nitrogen-atoms being bonded in the nitrogenous heteroaromatic.

8. electrophotography component (16 according to claim 7；24), wherein described be bonded to the substituent group of hydroxyl in institute Stating has alkylene oxide structure between the hydrogen atom of hydroxyl and the nitrogen-atoms.

9. electrophotography component (16 according to claim 8；24), wherein the alkylene oxide structure be by formula (I) or (II) structure indicated:

Wherein * indicates the binding site with the hydrogen atom of the hydroxyl；* indicates the binding site with the nitrogen-atoms；a For 1 or more and 9 integers below；And b is 1 or more and 4 integers below.

10. according to the described in any item electrophotography components (16 of claim 7-9；24), wherein the nitrogenous aromatic series is miscellaneous Ring cation is cationic selected from least one of glyoxaline cation and pyridylium.

11. according to the described in any item electrophotography components (16 of claim 7-9；24), wherein described can be with nitrogenous virtue The compound of fragrant race's heterocyclic onium cations reaction is selected from isocyanate compound, epoxide compound and melamine compound At least one of compound.

12. a kind of handle box (17) is detachably mounted to the main body of electronic photographing device and including charging member (24) At least one of with developer bearing member (16), which is characterized in that the charging member (24) or the developer bearing member Part (16) is according to the described in any item electrophotography components (16 of claim 1-11；24).

13. a kind of electronic photographing device comprising electrophotographic photosensitive element (18), charging member (24) and developer bearing member Part (16), which is characterized in that the charging member (24) or the developer bearing member (16) is according to claim 1-11 Described in any item electrophotography components (16；24).